Phosphonium salts and derivatives



United States Patent 3,214,434 PHOSPHONIUM SALTS AND DERIVATEVES MartinGrayson, Norwalk, Patricia Tarpey Keough, Ridgefield, and Michael McKayRauhut, Norwaik, Conn., assignors to American Cyanamid Company,Stamford, Conn., a corporation of Maine No Drawing. Original applicationFeb. 12, 1964, Ser. No. 344,224. Divided and this application Oct. 30,1964, Ser. No. 407,882

4 Claims. (Cl. 260-3065) The instant application is a division of US.application Serial No. 344,224, filed February 12, 1964, which in turnwas a continuation of US. application Serial No. 256,124 filed February4, 1963, now abandoned.

The present invention relates to organophosphorus compounds and to amethod of preparing same. More particularly, the instant discoveryconcerns phosphonium salt derivatives of tertiary phosphines.

It has been found that tertiary phosphines generally will react withhalo-substituted ethanol to produce the corresponding trialkyl-,tricycloalkyl-, or tri-aryl-Z-hydroxyethylphos-phonium salts. In turn,these salts may be acylated using a lower alkanoic anhydride, loweralkanoic acid, or the like, to produce their corresponding tria1kyl-,tricycloalkyl, or triaryl-Z-acetoxyethylphosphonium salts.

The following equations illustrate this general reaction:

( R R R POHZCH OHX esteritying agent 4 e 9 11 1mm cmornoy-x R R R eachrepresenting, as will be seen hereinafter,

alkyl, cycloalkyl and aryl,

X representing halogen or tetraphenyl borate, and

Y representing the residue of an acylating or esterifying agent. Thefollowing is a typical embodiment of generic Equations A and B, above:

The trialkyl-, tricycloalkyl-, and triaryI-Z-acetoxyethylphosphoniumsalts prepared as above may, in turn, be converted to theircorresponding vinylphosphonium salts according to the following generalEquation:

69 9 base 93 9 RIRZRQPCHZCHQOY-X R R R=PCH=CH -X in which R R R Y and Xare the same as above.

The following is a typical embodiment of Equation C, above:

NazCOz ice More specifically, in generic Equations A, B and C, above, RR and R each represent alkyl C C substituted alkyl C -C cycloalkyl, andaryl; X represents halogen, such as bromo, chloro and iodo, andtetraphenyl borate; and Y in Equations B and C represents the residue ofacylating agent as shown in the specific embodiments, supra.

Typical tertiary phosphine reactants are the following:trimethylphosphine, triethylphosphine, tripropylphosphine,tributylphosphine, tripentylphosphine, trihexylphosphine,triheptylphosphine, trioctylphosphine, trinonylphosphine,tridecylphosphine, triundecylphosphine, tridodecylphosphine,tritridecylphosphine, tritetradecylphosphine, tripentadecylphosphine,trihexadecylphosphine, dodecyldiethylphosphine, dioctylpropylphosphine,d'ietlrylbutylphosphiine, butylethylhexylphosphfine, tri(2-methoxypentyhphosphine, tris 2 cyanoethylphosphine,diethyl-Z-ethoxyheptylphosphine, tricyclopropylphosphinetricyclohexylphosphine, triphenylphos-phine, diphenylnaphthylphosphine,trixylylphosphine, tritolylphosphine, tris(para ethoxyphenyl)phosphine,tris(para chlorophenyl)phosphine, tris(2-chlorophenyl)phosphine, tris-(3-bromophenyl)phoshine, and the like.

Typical esterifying agents follow: lower alkanoic anhydrides, such asacetic anhydride, propionic anhydride, butanoic anhydride; loweralkanoic acids, such as formic acid, acetic acid, propionic acid,butanoic acid; acylating (C C alkanoyl) halides, such as acetylchloride, propionyl bromide, butyryl iodide, actanoyl chloride,dodecanoyl bromide, stearyl chloride, hexanoyl bromide; isopropenylacetate; aryl sulfonyl halides, such as paratoluenesulfonyl chloride,phenyl sulfonyl bromide, 2,4- dimethylphenylsulfonyl chloride; alkyl(lower) chloroformates, such as ethylchloroformate, butylchloroformate;alkyl (lower) carbonates, such as diethylcarbonate, dipropylcarbonate,dibutylcarbonate; ketene; dimethyl sulfate; nitrosyl chloride; andtrimethyl phosphate.

In Equation C, above, typical suitable inorganic and organic bases are:alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide,lithium hydroxide; alkali metal carbonates, such as sodium carbonate,potassium carbonate, lithium carbonate; alkaline earth metal hydroxides,such as magnesium hydroxide, barium hydroxide, calcium hydroxide;alkaline earth metal carbonates, such as magnesium carbonate, bariumcarbonate calcium carbonate; activated alumina; and quaternary ammoniumhydroxides, such as tetraalkyl (lower) ammonium hydroxides, includingtetramethylammonium hydroxide, tetrapropylammonium hydroxide, andtetrabenzylammonium hydroxide; and basic ion exchange resins.

The reaction in Equation A hereinabove is carried out at a temperaturein the range of 30 C. to 250 C., preferably 60 C. to 180 C. The EquationB reaction, above, is best carried out at a temperature in the range of5 C. to C. As to Equation C, above, this reaction is generally carriedout at a temperature in the range of 20 C. to C., preferably 50 C. to150 C.

Each of these three reactions may be carried out at atmospheric,sub-atmospheric or super-atmospheric pressure; preferably, however,reaction is carried out at at- 1 Typical are: polymeric quaternaryammonium salts, e.g., polymeric trimethylbenzyl ammonium chloride, etc.

mospheric pressure. By the same token, the ratio of the reactants ineach of Equations A, B and C is not critical, an excess of eitherreactant, in each equation, with respect to the other being suitable. InEquation B, however, an excess of about by weight of the acylating agentrelative to the phosphonium salt reactant is preferred. Generally inEquations A and C stoichiometric amounts of the reactants are employed.

The reactions of Equation A, above, are best carried out in the presenceof an inert organic solvent, i.e., a solvent which does not enter intoor otherwise inter- ,fere with the reaction under the conditionscontemplated herein. Typical solvents are dimethoxyethane, dioxane,ethylacetate, tetrahydrofuran, and the like.

The reactions of Equation B similarly are best carried out in thepresence of an inert organic solvent of the type described for EquationA, as well as acetic acid, dimethylformamide, diglyme, and the like.

As to Equation C, typical suitable inert organic solvents in which thephosphonium salt is soluble, which solvents do not interfere or enterinto reaction to any substantial degree, are dimethoxyethane, dioxane,dimethylformamide, diglyme, acetonitrile, ethylacetate, tetrahydrofuran,and other like linear and cyclic ethers, acetate esters (lower alkyl).

Alternatively, it has been found pursuant to the instant discovery thatthe products of Equation A, above, may

be converted directly to the products of Equation C,

thusly,

in the presence of any base given above for Equation C and at atemperature in the range of 100 C. to 250 C. As in Equation C, a solventof the type given hereinabove for Equation C is suitable and hereincontemplated. If desired, the reaction may be carried out in thepresence of a dehydrating agent, such as a siliceous agent includingsilica (e.g. silica gel), silica-alumina, and the like, in which otherinert organic solvents are also suitable, e.g. aromatic hydrocarbons,such as toluene, benzene, xylene, cymene, and the like, methylenechloride, ethylene chloride, etc.

The products of Equations A, B, C and D above are useful as fireretardants in plastics, e.g., from 0.5 to 30 parts by weight of any oneof above compounds when incorporated into 100 parts by weight of athermoplastic polymer material, such as polyethylene, polypropylene,polystyrene, polyacrylate, polymethylmethacrylate, or the like, providesenhanced fire retardance to the polymer material upon exposure to anopen flame.

While the following examples specify certain details as to certainembodiments of the present invention, it is not intended that thesedetails impose unnecessary limitations upon the scope of the instantdiscovery, excepting of course that these limitations appear in theappended claims.

EXAMPLE I T ributyZ-Z-hydroxyethylphosphonium tetraphenylborateTributyl-2-hydroxyethylphosphonium bromide, obtained from combiningtributylphosphine and 2-bromoethanol in 1,2-dirnethoxyethane andrefluxing under nitrogen, is dissolved in water and treated with excess0.1 N sodium tetraphenylboron. The resulting precipitate is filtered andrecrystallized from ethanol to yield product tributyl-'Z-hydroxyethylphosphonium tetraphenylborate with meltmg point 124C.-125 C. Analysis of product (found: C, 80.03; H, 9.00; P, 5.35. C H Orequires: C, 80.55; H, 9.25; P, 5.47%).

As is evident from this example, the halide salts of Equation A may beconverted, in situ or after recovery thereof, to the correspondingtetraphenylborate salts.

EXAMPLE II Tributyl-Z-acetoxyethylphosphonium bromide1,2-dimethoxyethane (275 milliliters), freshly distilled from calciumhydride, 2-bromoethanol (133 grams, 1.06 moles), and tributylphosphine(204 grams, 1.01 moles) are combined under nitrogen and refluxed at C.overnight with stirring. A heavy oil forms within an hour. Isopropenylacetate (320 grams, 3.2 moles) and 48% HBr (3 drops) are slowly added tothe reaction mixture which is then refluxed 18 hours. Volatilecomponents are removed in vacuo at 70 C. Product (372.5 grams; 99.9%yield) remains as a thick hygroscopic oil, which could be forced tocrystallize by stirring in a henzene-petroleum ether (boiling point 30C.-60 C.) mixture. Crystalline tributyl-2 acetoxyethylphosphonium saltis obtained from part of the oily product by freeze drying a benzenesolution of the oil.

EXAMPLE III Tributyl-Z-acet0xyethylpluosphonium tetraphenylborateTributyl-Z-acetoxyethylphosphonium bromide oil (16.2 grams produced asin Example II, above) is dissolved in water and treated with sodiumtetraphenylboron (15 grams) dissolved in water. A white precipitateappears which is filtered and recrystallized from ethanol containingenough acetonitrile to cause solution at the boiling point of themixture. Tributyl-Z-acetoxyethylphosphonium tetraphenylborate (16.7grams) is obtained with melting point of 177 C.179 C. Analysis ofproduct (found: C, 76.65; H, 8.83; P, 5.24. C H O BP requires: C, 78.93;H, 8.94; P, 5.10%).

EXAMPLE IV TriphenyI-Z-acetoxyethylphosphonium iodide 2-iodoethylacetate is prepared from the nucleophilic exchange reaction of sodiumiodide and 2-chloroethylacetate in refluxing acetone under nitrogen(boiling point 86 C.90 C. at 33 milliliters mercury). Triphenylphosphine(7.35 grams) is reacted with 2-iodoethylacetate (24 grams) undernitrogen with stirring at 80 C. for 4.5 hours. The excessZ-iodoethylacetate is distilled off in vacuo. Crude, brown crystallineproduct (14.20 grams) is obtained by washing oily residue with ether. Itis washed with ether, ethylacetate, and acetone and recrystallized fromacetonitrile to give product (7.90 grams) with melting point 161 C.-163C. Analysis of product (found: C, 55.16; H, 4.80; I, 26.77; P, 6.45. C HO IP requires: C, 55.47; H, 4.66; I, 26.66; P, 6.51%).

Example IV represents still another embodiment of the present inventionwherein the product salts of Equation B, above, are prepared directlyfrom the reaction of a 2-haloethyl acetate with a tertiary phosphine ofthe type contemplated herein.

The process of Example 1V, above, may be carried out using any of thetertiary phosphine reactants contemplated herein and the correspondingtri-substituted-2-acetoxyethylphosphonium halide produced and recovered,accordmg to the following equation O G) i] 9 R R RaPcH OH O -CH -Xwherein R R R and X have the meanings given hereinabove in Equations Aand B.

Equation E is best carried out at a temperature in the range of 5 C. to150 0, preferably at the reflux temperature of the solvent employed.Typical inert organic solvents contemplated for Equation E are acetone,lower alkanol (ethanol, butanol), plus the solvents listed hereinabovefor Equation C. The reaction under Equation E, as shown in Example IV,supra, is best carried out under inert conditions, such as undernitrogen. Other 2-haloethyl acetate reactants contemplated herein are2-bromoethyl acetate and 2-chloroethyl acetate.

Tables A, B, C, D and E, which follow, correspond to Equations A, B, C,D and E, respectively. The examples in Tables A and B are carried outessentially as in Examples I and II respectively, supra, excepting ofcourse as shown in Tables A and B. The examples in Table C are carriedout essentially as in Example LX, infra, excepting of course as shown inTable C. Likewise, the products of Table D are recovered essentially asin Example LX, infra. The examples in Table E are carried outessentially as in Example 1V, supra, excepting of course as shown inTable E.

Moles Moles XCH OH 0H Milli- I liters of solvent Solvent Product CH3 CH3CH3 I n-C Ha 11-04119 11-04119 1 VII..- VIIL.

l1-C4Hn Ill-04H II-CiHQ 11-C4H9 n-CiHq n-C 4H9 IX l-C4H9 l-C4H9 i-C Ho 1Cl n-C H n-CaHn II-CsHn 1 Cl 0am. oam. 0mm. 1 Cl XII.

XIIL- C111 CuHs CgHs 1 Cl XIV-. C4119 CzH5 CeHu 1 G1 I OH:

XV... C 115 GQHfl CzHsO-CH: 1 C1 XVI 1 XVII 1 Cl XVIII XXL- CHa- CHa CH31 Cl DME 1, 500 Z-hydroxyethyltrimethylphosphonium bromide.

2-hydroxyethyltributylphosphonium chloride.

D o 2-hydroxyethyltributylphosphonium iodideZ-hydroxyethyltriisobutyiphosphouium chloride.Z-hydroxyethyltrioctylphosphonium chloride.2-hydroxyethyitridodecylphosphonium chloride.2-hydroxyethyltrihexadecylphosphonium chloride.2-hydroxyethyltriethylphosphonium chloride. 2-hydroxyethylbutyiethylhexylphosphonium chloride DMEH." 1,500

1.1 DME 1. O Dioxane 200 1. 1 Ethyl 45 acetate.

1. 2 Dioxane..- 2-hydrox yethyldiethyl-2-ethoxyethylphosphoniumchloride.

1.3 DME. 1,600 2-hydroxyethyltricyciohexylphosphonium bromide.

0. 9 D ME... 2, 000 Z-hydroxyethyltricyciopentylphosphonium chloride.

1. 1 Dioxano... 2-hydroxyethyldiphenylnaphthylphosphonium iodide.

1.0 ..do..... 101 Z-hydroxyethyltriphenylphosphonium iodide.

l. 2 z-hydroxyethyltri(para-chlorophenyDphosphonium'chloride.

Ethyl acetate.

1. 3 DME... 1, 700 2-hydroxyethyltri (para-tolyl)- phosphonium chloride.

=- DME=dimethoxyethane. b THF=tetrahydroiuran.

TABLE B 1 6B 6 69 9 R R R PCH: CH1 OH-X+A R R R PCH; CH1 OY-X MolesExample Product of G) Solvent, Temp.,

No. Example R; PCH: A Moles A milliliters (1111.) 0. Product CH; OH-XXXII V 1. Isoproponyl acetate 3. 2 DME, 300 ml.- 832-icctgfigethyltrimethyl phosphonium 1'0 8. XXIII..-- VI 1. 0 DimcthylSulfate 3. 8 Dioxane, 300 ml. 90 2-methylsulfatoethyltributylphosphonium chloride. XXIV- VII 0. 8 Acetic anhydride 1. 0 Atlzgliicacid, 300 120 2-acleltoxgethyltributyl phosphonium c on e. XXV VIII 0.9Nitrosyl ch10ridc 1. 1 Diglyme 120 2-1i1it1rio1ethyltributyl phosphoniumo e. XXVI. IX 1. 0 Acctyl chloride. 1. 2 DME, 500 1111-..-2-aclvleltozicgethyltriisobutyl phosphonium c or e. XXVII. XI 1. 0p-Toluenesullonyl 1. 0 DME, 200 ml2-(p-toluenesulionyloxy)-ethyltrichloride. dodecylphosphonium chloride.XXVIII--. XIII 1. 0 Trimethyl phos- 1. 1 Acetic acid, 500 80Z-dimethylphosphatoethyltriethy] phate. ml. phosphonium chloride.XXIX"-.- XII 1. 0 Propionic acid 2. 4 DMF, 300 ml 10 Z-propionyloxyethyltrihexadecylphosphonium chloride. XXX XIV 1. 0 Butenoicenhydride. 1. 0 DMF, 1000 ml--- 30Z-butyryloxyethylbutylethylhexylphosphonium chlori e. XXXI XV 0. 8Acetic acid 4. 0 None 118 Z-acetoxyethyldiethyl-Z-ethoxyethylphosphoniumchloride. XXXII..-- XVI 0. 9 Acetyl chloride. 1. 0 DME, 200 ml...2-ricetoxyiethyltrlcyclohexylphosphonium r0 e. XXXIII.-. XVII 1. 0Hexanoyl chloride 1. 9 Dioxane, 150 ml. 252-hexanoyloxyethyltricyclopentylphosphouium chloride. XXXIV. XIX 1. 0Acetic enhydride. 6.0 None 100 2-ii1cgtoxyethyltriphenyl phosphonlum 0me. XXXV XVIII.- 1. 1 Stearyl chloride-.. 3. 3 DME, 700 m1 502-stearyloxyethyldiphenylnaphthylphosphonium lo de. XXXVI--- XX 1.0Dodecanoyl bro- 4.0 DMF, 1000 ml 402-dodecanoy1oxyethyltri(para-chloromide. phenyDphosphonium chloride.XXXVIL- XXI 1. 0 Phenylsulionyl 1. 0 Dioxane, 600 ml. 65Z-(phenylsulfonyloxy)ethlytri(para-toly1) bromide. phosphonium chloride.XXXVIII. V 1. 0 Ethylchloroformate- 2. 0 Diglyme, 300 ml. 402-(ethoxycarbonyloxy)ethyltrlmethyl phosphonium bromide. XXXIX--- VII 0.9 Dipropyl carbonate- 3. 0 DME, 250 ml---. 1002-(propoxycarbonyloxy)ethyltrlbutylphosphonium chloride. XL VII 1. 0Kotene 1. 0 THF, 500 1111.... Z-acetoxyethyltrlbutylphosphoniumchloride.

e mDMF=dimethylfamide.

TABLE 0 Example Product of Moles of Moles Solvent 2 Temp.,

N0. Example N 0. G9 6 Base of base milliliters (ml.) 0. ProductRIRZRSPCHQCHZOY'X XLI XXII 1. 0 K1003 1. 0 DME, 30 m1- 83Vigyltrignethylphosphonium [01111 e. XLII XXIII 1. 0 NeuCOa 2. 0Dioxanc, 300 m1- 100 vinhylltrgiutylphosphonium c on e. XLIII XXIV 1. 01112003 4. 0 M 15 1 a cetate, Do.

111 XLIV XXV 2.0 Mg(C0a) 8. 0 Digiyme Viinyltributylphosphonium o XLVXXVI 0. 5 Ba(OH)2 1. 0 Ace onitrile, 80 Vinyltriisobutylphosphon- 500ml. ium chloride. XLVI XXV II..--- 0. 9 Ca(OH)z 1.1 THF, 600 ml--.. 60Viinyltrildodgcylphosphonum 0 0].! e. XLVII.-.-. XXVIII.- 1. 0 Polymerictrimet hyl- 4. 0 DME, 400 ml 85 Vinyltriethylphosphonium benzyl ammoniumchloride. chloride. XLVIII XXIX 1. 0 X011 1. 0 THFVinyltrihexadecylphosphonium chloride. XLIX- XXX 1. 0 NaOH. 1. 0 Ar'efomfflle 20 Vinylbutylethylhexylphosphonium choride. L XXXI 1. 0LlOH 1. 0 d0 60 Vinyldiethyl-Z-ethoxyethylphosphonlum chloride. LIXXXII- 1. 0 Mg(OH)z 3.0 THF 72 Vinyltricyclohexylphosphonium bromide.LII XXXIII.-.- 2. 0 Ca(COa) 1. 0 Dloxane Vinyltricyclopentylphosphoniumchloride. LIII XXXIV.... 0.5 Ba(C0a) 1. 0 DME 81vilngltiriphenylphosphonium o e. LIV XXXV- 3. 0 Polymerictriethylbenzyl 1. 0 Dioxane 97 Vinlydiphenylnaphthylammonium hydroxide.phosphonium iodide. LV XXXvL... 1.0 do 5.0 DME 50Vinyltri(para-chlorophenyl) phosphonium chloride. LVI XXXVII.-. 1.0Actlvated alumina 1.0 THF 35 ,Vinyitrl(para,-tol 1) h honium choride.LVII XXXVIIL. 1.0 Tetramethylammonium 1.7 Diglyme 42 Viyltrimethylphosphonium hydroxide. bromide. LVIII XXXIX-.-- 2.0Tetrapropyl mmomum 1. 0 DMF 37 Vinyltributylphosphonium hydroxide.chloride. LIX XL 1. 0 Tctraberrzylammomum 1. 0 DME 25Vinyltributylphosphonium hydroxide. chloride.

h When not specified the amount of solvent employed is 500 milliliters.

TABLE D 69 6 base 69 9 R R R PCH OH OH-X--- R R R POH=CH X ExampleProduct of Base 7 Temp., Dehydrating agent 500 milliliters Product N 0.Example N 0. C. of solvent 1 VI. 1018 1003. 120 Silica gel BVinyltributylphosphonium chloride. 2 XI Ca(OH) 100 Silieafalumina eVinyltridodecylphosphonium chloride. 3 XII LinCO 220Vinyltrlhexadecylphosphonium chloride. 4 XV LiOFI 180 Silica-alumina BVinyldiethyl-2'ethoxyethyl-phosphonium chloride. 5 XVI Mg(OH) 150 Silicagel Vinyltricyclohexylphosphonium bromide. 6 XVIII NagCO: 250Vinyldiphenylnaphthylphosphonium iodide. 7 XIX 139.0 01 205Vinyltriphenylphosphonium iodide. 8 XX NagCOw 200Vinyltri(para-chlorophenyl)-phosphonium chloride. 9 XXI Activated 175Vinyltri(para-tolyDphosphonium chloride.

alumina.

e Finely-divided particulates.

TABLE E Example (E) Temp.,

N 0. ll C. Solvent Product R R R P+XCH CH,.0CCH3 TridodecylphosphineX=Br Refiux. Ethanol Tridodeeyl-2-acetoxyethylphosphonium bromide.Tricyclohexylphosphine X=I.-. AcetonitrTricyclohexyl-2-acetoxyethylphosphonium iodide.Tris(2-chlorophenyl)-phosphine- X=Cl-. Reflux Acetone Tris(Z-chlorophenyl)-2-acetoxyethylphosphonium chloride.Tris(Z-methoxypentyl)-phosphine X=I Dioxane 2-acetoxyethylphosphoniumiodide.

By finely-divided particles in Table D is intended 28 to 200 mesh.Larger or smaller particulates are likewise within the purview of theinstant discovery.

EXAMPLE LX Tributylvinylphosphonium bromide yield with melting point 148C.150 C.) Further recrystallization from ethylacetate-acetonitrileraises the molting point to 151.5 C. to 152.5 0.

Pursuant to the present discovery, the products of Tables B, C, D and E,hereinabove, may be converted to their corresponding sulfur-containingderivatives by reaction with sulfhydryl (e.g., an alkyl mercaptan, analkane dithiol, a benzencthiol, a dialkylphosphorodithioate, an0,0-dialkylphosphorodithioate, and the like) at a temperature in therange 20 C. to 200 C. Table F, G, H which follows illustrates thisreaction, the examples in said table being carried out essentially as inExample LXXVI, infra, excepting of course as specified in the table:

TABLE F, G, H

REAGTANTS PRODUCTS (F) ea 6 RIRZRQPCH=CHTX men QB 9 GB 9 base [R R RPCH; CH S] R-X mnm rcmcoiov-x msm.

(G) A 3 e9 9 \ll R1R1R3PCH=CHTX+ P311 8 A II/ A rumruromcmsr x s e Hbase A, RuvmPomomoYx+ PSH 9 0-2 R RR PCH=0H,-x l GsH Q z 0 Q e e R R RPCH CH SO x Q V 9 e C Z\ base \Q, a mmromomov-x o-srr 13 correspondingEquations A, B, C, D and E. The remaining symbols in equations F, G andH of Table F, G, H have the following meanings:

R represents alkyl or alkylene having from 1 to 12 carbon atoms; benzyl;trialkylsilyl in which the alkyl moiety has from 1 to 8 carbon atoms;benzene; toluene; xylene; and Z-naphthylene.

n is selected from 1 and 2.

A and A each represent lower alkyl and lower alkoxy.

Q and Q each represent H, lower alkyl, or, when taken together, theresidue of the phenyl radical.

Z represents S or 0.

As is evident from Table F, G, H, above the reactions contemplatedtherein using 2 acetoxyethylphosphonium salts as reactants are carriedout in the presence of a base of the type illustrated hereinabove forEquation C. By the same token, the vinylphosphonium salt reactants ofEquations F, G and H, respectively, of Table F, G, H may be reacted asshown in said table using or omitting a base. Furthermore, the solventsof Equation C, supra, are contemplated for the reactions of Equations F,G and H, as well as atmospheric, sub-atmospheric and superatmosphericconditions. Similarly, an excess of either reactant with respect to theother is contemplated, although stoichiometric amounts are generallyemployed. It will be noted from Table F, G, H (cm. particularly ExampleLXXI) that tertiary alkyl (lower) amines are likewise contemplated asbases. The amount of base used in the Examples of Table F, G, H is 1percent, based upon the total weight of reactants (1) and (2).Generally, from about .01 percent to about 10 percent may be used.

The products of Equations E, G, H are useful as fire retardants inplastics in the same manner described hereinabove for the productsEquations A, B, C and D.

Clearly, the instant discovery encompasses numerous modifications withinthe skill of the art. Consequently, while the present invention has beendescribed in detail with respect to specific embodiments thereof, it isnot intended that these details be construed as limitations upon thescope of the invention, except insofar as they appear in the appendedclaims.

We claim:

1. The compound of the formula wherein R R and R each represent a memberselected from the group consisting of alkyl C -C substituted alkyl C -Ccycloalkyl, phenyl, substituted phenyl, and naphthyl, said substituentsfor alkyl being selected from the group consisting of lower alkoxy andcyano and said substituents for phenyl being selected from the groupconsisting of lower alkyl and halogen;

X represents halogen;

Q and Q each represent a member selected from the group consisting ofhydrogen, lower alkyl, and when taken together, the residue of thephenyl radical;

Z represents a member selected from the group consisting of sulfur andoxygen.

2. The compound of the formula 3. A method which comprises bringing intoreactive contact a phosphonium salt of the formula and a sulfhydryl ofthe formula in the presence of an inert organic solvent and recover- 15ing the corresponding salt of the formula R R and R in the aboveformulae each represent a member selected from the. group consisting ofalkyl C -C substituted alkyl C C cycloalkyl, phenyl, substituted phenyl,and naphthyl, said substituents for alkyl being selected from the groupconsisting of lower alkoxy and cyano and said substituents for phenylbeing selected from the group consisting of lower alkyl and halogen;

X represents halogen;

Q and Q each represent a member selected from the group consisting ofhydrogen, lower alkyl, and when taken together, the residue of thephenyl radical;

Z represents a member selected from the group consisting of sulfur andoxygen.

4. A method which comprises bringing into reactive contact a phosphoniumsalt of the formula 40 G9 6 R R R PCHzCHgOY-X and a sulfhydryl of theformula in the presence of an inert organic solvent and a base andrecovering the corresponding salt of the formula rumauwrnoms-o X 15 16taken then together, the residue of the phenyl radical; Reid: OrganicChemistry of Bivalent Sulfur, vol. II Z represents a member selectedfrom the group con- (New York, 1960), pages 29 and 33-34.

sisting of sulfur and oxygen. Wagner et a1.: Synthetic Organic Chemistry(New York, 1953), pages 416-417.

References Cited by the Examiner Kosolapofi: Organophosphorus Compounds(New York, 1950), pages 83-84 and 88-89.

NICHOLAS S. RIZZO, Primary Examiner.

HENRY R. JILES, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No,3,214,454 October 26, 1965 Martin Grayson et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 2, line 29, for "actanoyl" read octanoyl lines 45 and 46, after"carbonate" insert a comma; columns 5 and 6 in the table, heading to theseventh column, for

"xca ca oa" read xca cn oa columns 7 and 8, TABLE 13,

Example No. XXXIV, last column thereof, for "iodine" read iodide sametable in the footnote, for "dimethylfamide read dimethylformamide same'columns, TABLE C, in the 69 G heading to the table for "MR R R PCH=CH -Xread (9 G R R R PCH=CH TX same table,in the heading to the sixth column,for "Solvent read Solvent columns 9 and 10, TABLE E, second column, line4 thereof, for "Tris(2methoxypentyl)phosphine" read Tri[2-methoxypentyl)phosphine finder "REACTANTS" in TABLE F for "R R R pcn co oy- X iR(SH)read R R R Pcn cn or-x R(SH) n columns ll and 12, in the table, firstcolumn, line 3 from the bottom, for "LXIII" read LXXIII column 12, lines71 and 72, the formula should appear as shown below instead of as in thepatent:

s i Q [(c n SP-CHZCHZSEUJCZHS) 1 1 column 13, line 27 for "cm." read cf,column 14, line 66, for "alkyll" read alkyl --n Signed and sealed this5th day of July 1966,

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J, BRENNER Attesting Officer Commissioner ofPatents

1. THE COMPOUND OF THE FORMULA
 3. A METHOD WHICH COMPRISES BRINGING INTOREACTIVE CONTACT A PHOSPHONIUM SALT OF THE FORMULAR1-P(+)(-R2)(-R3)-CH=CH2 X(-) AND A SULFHYDRYL OF THE FORMULAH5-C<(-Z-C(-Q)=C(-Q'')-N=) IN THE PRESENCE OF AN INERT ORGANIC SOLVENTAND RECOVERING THE CORRESPONDING SALT OF THE FORMULA(R1-P(-R2)(-R3)-CH2-CH2-S-C<(-Z-C(-Q)=C(-Q'')-N=))(+)X(-) R1, R2, AND R3IN THE ABOVE FORMULAE EACH REPRESENT A MEMBER SELECTED FROM THE GROUPCONSISTING OF ALKYL C1-C16, SUBSTITUTED ALKYL C1-C16, CYCLOALKYL,PHENYL, SUBSTITUTED PHENYL, AND NAPHTHYL, SAID SUBSTITUENTS FOR ALKYLBEING SELECTED FROM THE GROUP CONSISTING OF LOWER ALKOXY AND CYANO ANDSAID SUBSTITUENTS FOR PHENYL BEING SELECTED FROM THE GROUP CONSISTING OFLOWER ALKYL AND HALOGEN; X REPRESENTS HALOGEN; Q AND Q'' EACH REPRESENTA MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, LOWER ALKYL,AND WHEN TAKEN TOGETHER, THE RESIDUE OF THE PHENYL RADICAL; Z REPRESENTSA MEMBER SELECTED FROM THE GROUP CONSISTING OF SULFUR AND OXYGEN.
 4. AMETHOD WHICH COMPRISES BRINGING INTO REACTIVE CONTACT A PHOSPHONIUM SALTOF THE FORMULA R1-P(+)(-R2)(-R3)-CH2-CH2-O-Y X(-) AND A SULFHYDRYL OFTHE FORMULA HS-C<(-Z-C(-Q)-C(-Q'')-N=) IN THE PRESENCE OF AN INERTORGANIC SOLVENT AND A BASE AND RECOVERING THE CORRESPONDING SALT OF THEFORMULA (R1-P(-R2)(-R3)-CH2-CH2-S-C<(-Z-C(-Q)-C(-Q'')-N=))(+) X(-)WHEREIN R1,R2, AND R3 IN TH ABOVE FORMULAE EACH REPRESENT A MEMBERSELECTED FROM THE GROUP CONSISTING OF ALKYLL C1-C16, SUBSTITUTED ALKYLC1-C16, CYCLOALKYL, PHENYL, SUBSTITUTED PHENYL, AND NAPHTHYL, SAIDSUBSTITUENTS FOR ALKYL BEING SELECTED FROM THE GROUP CONSISTING OF LOWERALKOXY AND CYANO AND SAID SUBSTITUENTS FOR PHENYL BEING SELECTED FROMTHE GROUP CONSISTING OF LOWER ALKYL AND HALOGEN; X REPRESENTS HALOGEN; YREPRESENTS THE RESIDUE OF AN ESTERIFYING AGENT; Q AND Q'' EACH REPRESENTA MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, LOWER ALKYL,AND WHEN TAKEN THEN TOGETHER, THE RESIDUE OF THE PHENYL RADICAL; ZREPRESENTS A MEMBER SELECTED FROM THE GROUP CORSISTING OF SULFUR ANDOXYGEN.